Al-Azhar University- Gaza

Faculty of Science- Chemistry Department

Applied Chemistry

Solid lubricants
Solid Lubrication Fundamentals
and Applications

By:

Bassam F. Abutaweela

TO:

Dr. Hassan Tammous

Definition and Scope of Tribology:
Tribology is defined as "The science and technology of interacting
surfaces in relative motion, and of associated subjects and practices".
This term was introduced and defined in a report by a group set up by
the British Department of Education and Science. Tribology, having its
origin in the Greek word "xpt_o_," meaning rubbing or attrition, deals
with force transference between surfaces moving relative to each other.
This discipline includes such subjects as lubrication, adhesion, friction,
and wear of engineering surfaces with a view to understanding surface
interactions in detail (Fig. 1.1) and then prescribes improvements in
given applications. The technical function of numerous engineering
systems, such as machines, instruments, and vehicles, depends on
processes of motion. According to its basic physical definition the term
"motion" denotes the change in the position of an object with time.
Many processes in nature and technology depend on the motion and the
dynamic behavior of solids, liquids, and gases(Table 1.1). For example,
bearings and gears permit smooth, low-friction rotary or linear
movement between two surfaces (Fig. 1.2). Bearings employ either
sliding or rolling action and gears have both sliding and rolling action. In
these cases a strong attempt is made to provide enough lubrication to
keep the bearing and gear teeth surfaces separated by a film of solid
lubricant, oil, or other lubricant such as grease. The absence of physical
contact provides most bearings and gears with long service lives.
Tribology is a discipline that traditionally belongs to mechanical
engineering. However, with the recent push toward higher speeds,
loads, and operating temperatures, longer term life, lighter weight and
smaller size, and harsh environments in mechanical, mechatronic, and
biomechanical systems, the field of tribology is becoming more and
more interdisciplinary, embracing physics, chemistry, metallurgy,
biology, and engineering.
Social and Economic Impact of Tribology:
The subject of tribology is identified as one of great importance; yet
largely because of its multidisciplinary nature, it has received insufficient
attention. As a direct result mechanical engineering design is retarded,
and many tens of billions of dollars have unnecessarily been lost each
year through friction, wear, related breakdowns, wasted energy, etc.
These costs are the direct costs of friction and wear. Consideration must
also be given to the indirect costs, such as loss of production, product
liabilities, failure to accomplish a significant mission, or standby
maintenance costs. Some classical estimates of economic losses due to
tribology and savings through tribology are presented in Table 1.2. The
final report of the National Commission on Materials Policy to the
Congress of the United States (as reported by Ballard in 1974) stated
that "material losses due to tribology (friction and wear) cost the U.S.
economy $100 billion per year, with a material component of this loss of
about $20 billion. At that time Rabinowicz also estimated the total U.S.
cost of wear to be $100 billion per year. In 1978 the National Bureau of
Standards (presently, the National Institute of Standards and
Technology) estimated $70 billion for corrosion and $20 billion for wear
(ref. 1.6). Peterson estimated that the cost of wear of naval aircraft and
ships per year is approximately two-thirds the fuel cost. These figures
indicate that the cost of tribological losses is large and should be
reduced by national efforts. Jost, of the United Kingdom, suggested that
with research efforts it is comparatively easy and inexpensive to save up
to 20 percent of tribological losses. For example, for the United States
the calculated savings would have been $12 billion to $16 billion per
year in 1974. It is not surprising that estimates of financial savings for
the United States in 1977 are significantly larger, and range .
from $16 billion to more than $40 billion per year (refs. 1.9 and 1.10). It
is now believed that proper attention to tribology, especially in
education, research, and application, could lead to economic savings of
between 1.3 and 1.6 percent of the gross national product (GNP) (ref.
1.8). Thus, tribology impacts strongly on the national economy and on
the lifestyles of most people. Wear contributes to short product lives
and friction contributes to energy consumption. As material and energy
shortages develop, there will be greater demand for longer product
lives, increased wear resistance, and reduction in energy consumption
through lubrication and accordingly lower friction. The most effective
way to reduce friction and wear is to separate the two sliding surfaces
by means of a lubricating film (third body), such as a film of solid
lubricant, oil, grease or gas.
Elements of machines, such as bearings(plain, rolling element, slides,
guides , and ways) ,gears ,cylinders ,flexible couplings, chains ,cams and
cam followers, and wire ropes, have fitted or formed surfaces that move
with respect to each other by sliding ,rolling ,approaching and receding,
or combinations of these motions. Therefore, these elements are
lubricated to prevent or reduce the actual contact between surfaces.
Moving surfaces of machine elements are lubricated by interposing and
maintaining films that minimize actual contact between the surfaces and
that shear easily so that he frictional force opposing surface motion is
low. If actual contact between surfaces occurs, high frictional forces
leading to high temperatures and wear will result. Without lubrication
most machines would run for only a short time. With inadequate
lubrication excessive wear is usually the most serious consequence,
since a point will be reached, usually after a short period of operation,
when the machine elements cannot function and the machine must be
taken out of service and repaired. Repair costs (material and labor) may
be high, but lost production or lost machine availability may be by far
the greatest cost .With inadequate lubrication, even before elements
fail, frictional forces between surfaces may be so great that drive motors
will be overloaded or frictional power losses will be excessive. Finally,
with inadequate lubrication machines will not run smoothly and quietly.

Historical Perspective of Tribology and Solid Lubricants:

Historical factors have influenced the development of tribology, in
particular solid lubricants. This brief perspective will help the reader
understand the present state of the science and technology of this field.
The details of the history of tribology, including lubricants and
lubrication, can be found in the literature. We live in a solid world. The
earth itself is solid; the stones and sands on its surface are solid; people
and their tools and their machines are solid. These solids are in contact
with each other. Whenever two solids touch each other so that forces of
action and reaction are brought into play, the solids may be said to
undergo a surface interaction. Naturally, the history of tribology spans a
period similar to that of recorded history. Important tribological
developments occurred in prehistoric and early historic times. The first
civilization recorded in the history of humanity developed in the fourth
millennium B.C., probably about 3500 B.C., in a territory known as
Sumer adjacent to the Persian Gulf at the southern end of Mesopotamia.
Somewhat later, Egyptian civilization flourished. Five recorded
accomplishments of the Sumerian and Egyptian civilizations (3500 B.C.
to 30 B.C.) are of great tribological significance:

1. Drills employing alternating rotary motion and simple beatings were

developed for making fire and drilling holes.

2. The potter's wheel ,employing simple pivot bearings made from

wood or stone, was produced to facilitate the throwing of clay at
relatively high rotational speeds.

3. The wheeled vehicle appeared.

4. Heavy stone statues and building blocks were transported on

sledges.

5. Lubricants were used in a number of applications involving rotation

and translation.
Lubricants were mainly of vegetable or animal origin. A most interesting
story related to the early use of lubricants comes from the building of
the pyramids in the third millennium B.C. Hydrated calcium sulphate
(gypsum) was used to form the thin bed of viscid mortar. The mortar
acted as a lubricant to facilitate accurate setting of the huge blocks of
stone. Clearly, tribology and the use of lubricants date back to the first
recorded civilization. Since this early beginning lubrication and the
production of lubricating media have grown to be one of the largest
industries in the world, yet from one-third to one-half of all the energy
produced still is lost through friction. Although the slippery feel and
appearance of graphite has been known for centuries, its use as a solid
lubricant probably dates back to the Middle Ages. Graphite is also
known as black lead and plumbago. It was long confused with similar-
appearing minerals, particularly molybdenite (MoS2), and was not
classified as a separate mineral until 1556. In 1779 it was proved to be
carbon when it was oxidized to carbon dioxide. About 1564 the
Borrowdale graphite mines in England began producing graphite for
pencils. These early pencils were made by encasing slabs of cut graphite
in slotted wooden dowels. The name "graphite" did not come into being
until 1789, when Werner drew it from the Greek word "graphein,"
which means to write. The ore molybdenite was known to the early
Greeks. It has often been confused with graphite and with lead. The
name is derived from the Greek word meaning lead.

Traditional animal and vegetable sources satisfied the ever-increasing

demand for lubricants throughout the Industrial Revolution. A selection
of the lubricants most commonly employed during the Industrial
Revolution is listed in Table 1.3. It is commonly thought that solid
lubricants are a relatively recent phenomenon, but their use in the
lubrication of heavy, slow-moving machinery was well established
during the Industrial Revolution. One of the first patents, issued in 1812,
describes the use of graphite, pork lard, beef suet, mutton suet, tallow,
oil, goose grease, or any kind of grease or greasy substance as
lubricants. Also, instructions were given on the methods of application
and amounts of the composition to be used in bearings, steam-engine
piston rods, and the stone spindles of mills. The first extensive technical
investigation was by Rennie, who, in 1829, measured coefficients of
friction with various solid materials as lubricants. In the 1800's a variety
of solid lubricants were used in metal-working applications.
Molybdenum is widely distributed over the Earth's crust in the form of
molybdenite. The largest commercial source of the mineral is in Climax,
Colorado, where it is mined from granite containing the ore in a finely
divided state. Molybdenum disulfide has a metallic luster and is blue-
gray to black. Early pioneers traveling through the Climax area used
pulverized rock to lubricate the wheels on their Conestoga wagons. This
probably was one of the first uses of MoS , a solid lubricant in the
United States. The selection of liquid lubricants changed dramatically in
the mid-eighteenth century when the first oil well was drilled in
Titusville, Pennsylvania, in 1859. Mineral oils, which had previously been
available only in relatively small volumes by distillation from shale,
emerged in large quantities from flowing and pumping wells to form the
major source of lubricants. The 1850's witnessed a far-reaching
transition in the origin of lubricants and the start of a petroleum
industry that was to support and be vital to industrial expansion in the
nineteenth and twentieth centuries. The technology of lubrication
advanced rapidly. During the mid-1930's petroleum oils were improved
through the use of additives, which increased their load-carrying ability,
lubricating properties, corrosive protection, and thermal oxidation
stability. A trend also developed that required moving parts to operate
at higher and higher temperatures. Because petroleum oils could not
adequately do the job at these high temperatures, synthetic lubricant
materials were introduced. Temperatures now encountered in
supersonic aircraft, spacecraft, and certain industrial applications are
beyond the useful range of even the synthetic lubricants. This trend to
the operation of bearing surfaces at higher temperatures and low
pressures has led to the development and use of solid lubricants to
attain the necessary lubrication. Solid lubricants have at least one very
desirable feature--they do not evaporate under the aforementioned
conditions. A solid lubricant can generally be defined as a material that
provides lubrication, under essentially dry conditions, to two surfaces
moving relative to each other. The most common dry solid lubricants
are graphite, MoS2, WS2, and PTFE. The use of bonded, solid lubricant
materials is relatively new. The first U.S. patent for a bonded material
(phosphoric-acid-bonded graphite film) was issued in the mid1940's.
Several hundred patents for solid lubricating materials and binders have
been issued so far. The use of molybdenum disulfide as a lubricating
solid also began in the 1940's, and MOS2 is now used in more
applications than any other lubricating solid. On April 6, 1938, Piunkett
was investigating the results of a failed experiment involving
refrigeration gases when he found a white, waxy substance. The
material, polytetrafluoroethylene, commonly known as Teflon, has
proved inert to virtually all chemicals. It also is one of the most slippery
dry materials known. The study and application of solid lubricants as
they are now known is a relatively new field. No systematic study of
these materials was begun until long after they were introduced in the
aircraft industry. In the 1950's, with the development of the jet engine,
a number of research laboratories began a systematic study of solid
lubrication for high temperatures. Most of the work was directed
toward defining the required characteristics of solid lubricants. In the
1960's space lubrication needs prompted increased research into solid
lubrication with emphasis on the role of atmosphere. Ways of using
solid lubricants were explored. By the early 1970's, when many of the
problems had been resolved and their limitations defined, most of the
research stopped. Recently, however, a number of new applications
have arisen that have prompted renewed interest. These applications
are piston tings for low-heat-rejection engines, lubricating cages for
advanced gas turbines, gears and bearings for long-term service in space
mechanisms, cages for turbo pump bearings operating in liquid
hydrogen and oxygen, lightweight gear and bearing systems, and low-
cost bearing systems for automobiles and industrial machinery. The new
requirements are primarily long-term life and broad-temperature-range
capability. New solid lubricants are needed that meet these
requirements. Lastly, although the importance of friction and resistance
to motion has no doubt been recognized throughout the ages, a full
appreciation of the significance of tribology in a technological society is
a recent phenomenon.
Description of Solid and Liquid Lubrication:
Lubricating films are classified as three types: solid films, fluid films, and
thin films (Table 1.4). They are described briefly here, but more details
can be found in the literature.

Solid Films:

A solid lubricant is defined as "any material used as a thin film or a

powder on a surface to provide protection from damage during relative
movement and to reduce friction and wear." Solid lubrication is
achieved by self-lubricating solids or by imposing a solid material having
low shear strength and high wear resistance between the interacting
surfaces in relative motion. The solid material may be a dispersion in
oils and greases, a loose powder, or a coating. Solid lubricants are used
when liquid lubricants do not meet the advanced requirements of
modem technology. They are less expensive than oil and grease
lubrication systems for many applications. Solid lubricants also reduce
weight, simplify lubrication, and improve materials and processes.
Examples of applications needed to meet critical operating conditions
are presented in Fig. 1.3 and Table 1.5(a). Figure 1.3 and Table 1.5 list
solid lubricant applications for which fluid lubricants are ineffective and
undesirable. Changes in critical environmental conditions, such as
pressure, temperature, and radiation, affect lubricant efficiency.
Further, in the cost-conscious automotive industry, solid lubricants are
replacing oils and greases in many applications and helping to make
highly efficient automobiles possible. Oils or greases cannot be used in
many applications because of the difficulty in applying them, sealing
problems, weight, or other factors, such as environmental conditions.
Solid lubricants may be preferred to liquid or gas films for several
reasons. In high-vacuum environments, in space-vacuum environments,
or in food processing machines, a liquid lubricant would evaporate and
contaminate the product, such as optical and electronic equipment or
food. At high temperatures liquid lubricants decompose or oxidize;
suitable solid lubricants can extend the operating temperatures of
sliding systems beyond 250 or 300 °C while maintaining relatively low
coefficients of friction. At cryogenic temperatures liquid lubricants are
highly viscous and are not effective. Under radiation or corrosive
environments liquid lubricants decompose or will be contaminated.
Further, in the weight conscious aerospace industry, solid lubricants
lead to substantial weight savings.
with respect to the use of liquid lubricants. The elimination (or limited
use) of liquid lubricants and their replacement by solid lubricants affect
aircraft or spacecraft weight and therefore have a dramatic impact on
mission extent and craft maneuverability. Under high vacuums, high
temperatures, cryogenic temperatures, radiation, or space or corrosive
environments, solid lubrication may be the only feasible system.
Numerous solid lubricants, such as permanently bonded lubricating films,
have been developed to reduce friction and wear in applications of this
type where fluid.
 lubricants are ineffective and undesirable. The simplest kind of solid
lubricating film is formed when a low-friction solid lubricant, such as
molybdenum disulfide (MoS2), is suspended in a carder and applied to the
surface like a normal lubricant. The carder may be a volatile solvent, a
grease, or any of several other types of material. After the carrier is
squeezed out or evaporates from the surfaces, a layer of MoS2 provides
lubrication. Solid lubricants are also bonded to rubbing surfaces with
various types of resin, which cure to form strongly adhering coatings with
good frictional properties.
In some plastic bearings the solid lubricant is sometimes incorporated
into the plastic. During operation some of the solid lubricant may be
transferred to form a lubricating coating on the mating surface. In
addition to MoS2, polytetrafluoroethylene (PTFE), polyethylene, and a
number of other materials are used to form solid films. Sometimes,
combinations of several materials, each contributing specific properties
to the film, are used. Because of recent innovations in the physical and
chemical vapor deposition processes, solid lubricating materials, such as
MoS2, tungsten disulfide (WS2), diamond, and PTFE films, are grown
economically on ceramics, polymers, and metals and used as solid
lubricating films.
Fluid Films:

Fluid film lubrication is the most desirable form of lubrication, since

during normal operation the films are thick enough to completely
separate the load-carrying surfaces. Thus, friction is at a practical
minimum, being due only to shearing of the liquid lubricant films; and
wear does not occur, since there is essentially no mechanical contact.
Fluid films are formed in three ways: hydro dynamically, hydrostatically,
and by squeezing (Table 1.4). Hydrodynamic films.--The most effective
way to separate two sliding surfaces by means of a fluid and to reduce
friction and wear is known as hydrodynamic lubrication. It provides
coefficients of friction on the order of 0.003, or less, depending on the
sliding velocity, load, and fluid viscosity. It eliminates wear entirely,
since the solids do not touch or collide with each other. Gyroscope
bearings are one example where the ideal conditions of hydrodynamic
lubrication are substantially achieved. Two types of hydrodynamic film
lubrication are now recognized: thick hydrodynamic films and
elastohydrodynamic films (Table 1.4). Plain journal bearings and tilting-
pad or tapered-land thrust bearings (Figs. 1.2(a) and 1.4) have thick
hydrodynamic films, usually more than 25 _tm thick. In applications the
loads are low enough, and the areas over which the loads are
distributed are large enough, that the load-carrying area does not
deform enough to significantly alter that area. Load-carrying surfaces of
this type are often referred to as "conforming" although it is obvious
that in tapered-land thrust bearings, for example, the surfaces do not
conform in the normal concept of the word. However, the term is a
convenient opposite for the term "nonconforming," which quite
accurately describes the types of surface where elastohydrodynamic
films are formed. The surfaces of the balls in a ball beating theoretically
make contact with the raceways at points; the rollers in a roller bearing
make contact with the raceways along lines; and meshing gear teeth
also make contact along lines (e.g., Figs. 1.2(b) and (c)). These types of
surface are nonconforming. Under the pressures applied.
to these elements by the lubricating film, however, the metals deform
elastically, expanding the theoretical points or lines of contact into
discrete areas. Since a convergent zone exists immediately before these
areas of contact, a lubricant will be drawn into the contact area and can
form a hydrodynamic film. This type of film is referred to as an
"elastohydrodynamic film." The "elasto" part of the term refers to the
fact that elastic surface deformation must occur before the film can be
formed. This type of lubrication is elastohydrodynamic lubrication (EHL),
a condition of lubrication in which the friction and film thickness
between two surfaces in relative motion are determined by the elastic
properties of the surfaces in combination with the viscous properties of
the lubricant. The viscous properties include variation of viscosity with
pressure, temperature, and shear rate. EHL films are very thin, on the
order of 0.25 to 1.25 _tm thick. However, even with these thin films,
complete separation of the contacting surfaces can be obtained. Any
material that will flow at the shear stresses available in the system may
be used for fluid film lubrication. In most applications petroleum-
derived lubricating oils are used. There are some applications for
greases. Some materials not usually considered to be lubricants, such as
liquid metals, water, and gases, are also used. For example, magnetic
recording is accomplished by relative motion between a magnetic
medium and a magnetic head (Fig. 1.5); under steady operating
conditions a load-carrying hydrodynamic gas (air) film is formed

Ideal conditions of hydrodynamic lubrication can rarely be maintained

in practice. Starting, stopping, misalignment, heavy loads, and other
service conditions can cause the fluid film to be squeezed out or allow
the surface asperity to break through the film, so that the two solids are
pressed into contact with one another. Even in modem high-end
computer tape and disk drives, there is physical contact between the
medium and the head during starting and stopping. Ideal hydrodynamic
lubrication then ends, and boundary lubrication, or lubrication by solids,
begins.

Hydrostatic films: In hydrostatic film lubrication the pressure in the fluid

film that lifts and supports the load is provided from an external source.
Thus, relative motion between opposing surfaces is not required to
create and maintain the fluid film. The principle is used in plain and flat
bearings of various types, where it offers low friction at very low speeds
or when there is no relative motion; more accurate centering of a
journal in its bearing; and freedom from stick-slip effects. The simplest
type of hydrostatic bearing is illustrated in Fig. 1.6. Oil under pressure is
supplied to the recess or pocket. If the supply pressure is sufficient, the
load will be lifted and floated on a fluid film. The total force developed
by the pressure in the pocket and across the lands will be such that the
total upward force is equal to the applied load. The clearance space and
the oil film thickness will be such that all the oil supplied to the bearing
can flow through the clearance spaces under the pressure conditions
prevailing. Squeeze films.--As the applied pressure on an oil increases,
its viscosity increases. This fact contributes to the formation of what are
called squeeze films.

The principle of the squeeze film is shown in Fig. 1.7(a), where

application of a load causes plate A to move toward stationary plate B.
As pressure develops in the oil layer, the oil starts to flow away from the
area. However, the increase in pressure also increases the oil viscosity,
so that the oil cannot escape as rapidly and a heavy load can be
supported for a short time. Sooner or later, if load continues to be
applied, all the oil will flow or be forced from between the surfaces and
metalto-metal contact will occur, but for short periods such a
lubricating film can support very heavy loads. One application where
squeeze films are formed is in piston pin bushings (Fig. 1.7(b)). At the
left the load is downward on the pin and the squeeze film develops at
the bottom. Before the film is squeezed so thin that contact can occur,
the load reverses (right view) and the squeeze film develops at the top.
The bearing oscillates with respect to the pin, but this motion probably
does not contribute

much to film formation by hydrodynamic action. Nevertheless, bearings

of this type have high load-carrying capacity.
Effect of viscosity, speed, and load:

The oil film (wedge) formed in a hydrodynamic bearing is a function of

speed, load, and oil viscosity. Under fluid film conditions an increase in
viscosity or speed increases the oil film thickness and the coefficient of
friction; an increase in load decreases them. It is now generally
accepted that the coefficient of friction _t can be shown by a curve such
as that in Fig. 1.8. The coefficient of friction is plotted as a function of a
single dimensionless factor, viscosity times velocity divided by load. A
similar type of curve could be developed experimentally for any fluid
film bearing. The curve is also called the Stribeck curve. The accurate
experimental measurements of Stribeck from 1900 to 1920 served as a
basis for the theoretical work of many researchers in establishing the
theory of hydrodynamically lubricated bearings. In Fig. 1.8 three main
lubrication regimes may be distinguished:

1. Fluid film lubrication (thick hydrodynamic lubrication,

elastohydrodynamic lubrication, etc.) exists in the zone to the
right of c.
2. Mixed film lubrication or partial elastohydrodynamic lubrication
(EHL) exists in the portion of the curve between a and c, including
the minimum value of kt to the dimensionless value indicated by
b.
3. Boundary lubrication exists to the left of a, where conditions are
such that a full fluid film cannot be formed, some friction and wear
commonly occur, and very high coefficients of friction may be
reached.

Mixed film lubrication and boundary lubrication are discussed next.

Thin Films:

A copious, continuous supply of liquid lubricant is necessary to maintain

fluid films. In many cases it is not practical or possible to provide such
an amount of lubricant to machine elements. In other cases, as for
example during starting of a hydrodynamic film bearing, loads and
speeds are such that fluid films cannot be maintained. Under these
conditions lubrication is by what are called thin films. When surfaces
run together under thin film conditions, enough oil is often present so
that part of the load is carried by fluid films and part is carried by
contact between the surfaces. This condition is often called mixed film
lubrication. With less oil present, or with higher loads, a point is reached
where fluid oil plays little or no part. This condition is often called
boundary lubrication, the condition of lubrication in which the friction
and wear between two surfaces in relative motion is determined by the
properties of the surfaces and by the properties of the lubricant other
than bulk viscosity. Many circumstances that are referred to as
"boundary lubrication" are in fact elastohydrodynamic. When rubbing
(sliding) contact is made between the surface peaks, known as
asperities, a number of actions take place, as shown in Fig. 1.9, which
represents a highly magnified contact area of two surfaces:

1. At a in Fig. 1.9, sliding surfaces completely separate and thick films

are formed. Friction at a is due only to shearing of the liquid
lubricant films.
2. There is heavy rubbing at b, as surface films are sheared, and elastic
or plastic deformation occurs. Real (in contrast to apparent) areas of
contact are extremely small and unit stresses are very high.

3. As some areas at c are rubbed or sheared, the clean surfaces weld

together. The minute welds break as motion continues. But
depending on their strength, the welds may break at another
section so that metal is transferred from one member to the other.
4. The harder shaft material plows through the softer bearing material
at d, breaking off wear particles and creating new roughnesses.

These actions account for friction and wear in boundary lubrication.